Thirdly. Such a temperature that the unstable compound may form at the surface, where the aëriform constituent is present in large mass, while it decomposes at the opposite surface, where the quantity is less abundant.
One of the most remarkable results of Graham's study of this peculiar mode of transfer of aëriform matter through the very substance of solid bodies was an ingenious method of separating the oxygen from the atmosphere. The apparatus consisted simply of a bag of India-rubber kept distended by an interior framework, while it was exhausted by a Sprengel pump. Under these circumstances the selective affinity of the caoutchouc determines such a difference in the rate of transfer of the two constituents of the atmosphere that the amount of oxygen in the transpired air rises to forty per cent., and by repeating the process nearly pure oxygen may be obtained. It was at first hoped that this method might find a valuable application in the arts, but in this Graham was disappointed; for the same result has since been effected by purely chemical methods, which are both cheaper and more rapid.
These experiments on India-rubber naturally led to the study of similar effects produced with metallic septa, which, although to some extent previously observed in passing gases through heated metallic tubes, had been only imperfectly understood. Thus, when a stream of hydrogen or carbonic oxide is passed through a red-hot iron tube, a no inconsiderable portion of the gas escapes through the walls. The same is true to a still greater degree when hydrogen is passed through a red-hot tube of platinum, and Graham showed that, through the walls of a tube of palladium, hydrogen gas passes, under the same conditions, almost as rapidly as water through a sieve. Moreover, our distinguished associate proved that this rapid transfer of gas through these dense metallic septa was due, as in the case of the India-rubber, to an actual chemical combination of its material with the metal, formed at the surface, where the gas is in excess, and as rapidly decomposed on the opposite face of the septum. He not only recognized as belonging to this class of phenomena the very great absorption of hydrogen by platinum plate and sponge in the familiar experiment of the Doebereiner lamp, but also showed that this gas is a definite constituent of meteoric iron—a fact of great interest from its bearing on the meteoric theory.
We are thus led to Graham's last important discovery, which was the justification of the theory we have been considering, and the crowning of this long line of investigation. As may be anticipated from what has been said, the most marked example of that order of chemical compounds, to which the metallic transpiration of aëriform matter we have been considering is due, is the compound of palladium with hydrogen. Graham showed that, when a plate of this metal is made the negative pole in the electrolysis of water, it absorbs nearly one thousand times its volume of hydrogen gas—a quantity approximatively equivalent to one atom of hydrogen to each atom of palladium. He further showed that the metal thus becomes so profoundly altered as to indicate that the product of this union is a definite compound. Not only is the volume of the metal increased, but its tenacity and conducting power for electricity are diminished, and it acquires a slight susceptibility to magnetism, which the pure metal does not possess. The chemical qualities of this product are also remarkable. It precipitates mercury from a solution of its chloride, and in general acts as a strong reducing agent. Exposed to the action of chlorine, bromine, or iodine, the hydrogen leaves the palladium and enters into direct union with these elements. Moreover, although the compound is readily decomposed by heat, the gas can not be expelled from the metal by simple mechanical means.
These facts recall the similar relations frequently observed between the qualities of an alloy and those of the constituent metals, and suggest the inference made by Graham, that palladium charged with hydrogen is a compound of the same class—a conclusion which harmonizes with the theory long held by many chemists, that hydrogen gas is the vapor of a very volatile metal. This element, however, when combined with palladium, is in a peculiarly active state, which sustains somewhat the same relation to the familiar gas that ozone bears to ordinary oxygen. Hence Graham distinguished this condition of hydrogen by the term "hydrogenium." Shortly before his death a medal was struck at the Royal Mint from the hydrogen palladium alloy in honor of its discovery; but, although this discovery attracted public attention chiefly on account of the singular chemical relations of hydrogen, which it brought so prominently to notice, it will be remembered in the history of science rather as the beautiful termination of a life-long investigation, of which the medal was the appropriate seal.
Simultaneously with the experiments on gases, whose results we have endeavored to present in the preceding pages, Graham carried forward a parallel line of investigation of an allied class of phenomena, which may be regarded as the manifestations of molecular motion in liquid bodies. The phenomena of diffusion reappear in liquids, and Graham carefully observed the times in which equal weights of various salts dissolved in water diffused from an open-mouth bottle into a large volume of pure water, in which the bottle was immersed. He was not, however, able to correlate the results of these experiments by such a simple law as that which obtains with gases. It appeared, nevertheless, that the rate of diffusion differs very greatly for the different soluble salts, having some relation to the chemical composition of the salt which he was unable to discover. But he found it possible to divide the salts into groups of equi-diffusive substances, and he showed that the rate of diffusion of the several groups bear to one another simple numerical ratios.
More important results were obtained from the study of a class of phenomena corresponding to the transpiration of gases through India-rubber or metallic septa. These phenomena, as manifested in the transfer of liquids and of salts in solution through bladder or a similar membrane, had previously been frequently studied under the names of exosmose and endosmose, but to Graham we owe the first satisfactory explanation. As in the case of gases, he referred these effects to the influence of chemical force, combination taking place on one surface of the membrane and the compound breaking up on the other, the difference depending, as in the previous instance, on the influence of mass. He also swept away the arbitrary distinctions made by previous experimenters, showed that this whole class of phenomena are essentially similar, and called this manifestation of power simply "osmose."
While studying osmotic action, Graham was led to one of his most important generalizations—the recognition of the crystalline and amorphous states as fundamental distinctions in chemistry. Bodies in the first state he called crystalloids; those in the last state, colloids (resembling glue). That there is a difference in structure between crystalloids, like sugar or felspar, and colloids, like barley candy or glass, has of course always been evident to the most superficial observer; but Graham was the first to recognize in these external differences two fundamentally distinct conditions of matter not peculiar to certain substances, but underlying all chemical differences, and appearing to a greater or less degree in every substance. He showed that the power of diffusion through liquids depends very much on these fundamental differences of condition—sugar, one of the least diffusible of the crystalloids, diffusing fourteen times more rapidly than caromel, the corresponding colloid. He also showed that, in accordance with the general chemical rule, while colloids readily combine with crystalloids, bodies in the same condition manifest little or no tendency to chemical union. Hence, in osmose, where the membranes employed are invariably colloidal, the osmotic action is confined almost entirely to crystalloids, since they alone are capable of entering into that combination with the material of the septum on which the whole action depends.
On the above principles Graham based a simple method of separating crystalloids from colloids, which he calls "dialysis," and which was a most valuable addition to the means of chemical analysis. A shallow tray, prepared by stretching parchment paper (an insoluble colloid) over a gutta-percha hoop, is the only apparatus required. The solution to be "dialyzed" is poured into this tray, which is then floated on pure water, whose volume should be eight or ten times greater than that of the solution. Under these conditions the crystalloids will diffuse through the porus septum into the water, leaving the colloids on the tray, and in the course of a few days a more or less complete separation of the two classes of bodies will have taken place. In this way arsenious acid and similar crystalloids may be separated from the colloidal materials with which, in the case of poisoning, they are usually found mixed in the animal juices or tissues.
But, besides having these practical applications, the method of dialysis in the hands of Graham yielded the most startling results, developing an almost entirely new class of bodies, as the colloidal forms of our most familiar substances, and justifying the conclusion that the colloidal as well as the crystalline condition is an almost universal attribute of matter. Thus, he was able to obtain solutions in water of the colloidal states of aluminic, ferric, chromic, stannic, metastannic, titanic, molybdic, tungstic, and silicic hydrates, all of which gelatinize under definite conditions like a solution of glue. The wonderful nature of these facts can be thoroughly appreciated only by those familiar with the subject, but all may understand the surprise with which the chemist saw such hard, insoluble bodies as flint dissolved abundantly in water and converted into soft jellies. These facts are, without doubt, the most important contributions of Dr. Graham to pure chemistry.